Process for the catalytic hydrogenation of unsaturated compounds and catalyst employable in such a process

ABSTRACT

The present invention refers to a process for the catalytic hydrogenation of unsaturated compounds using as catalyst an acetylenic complex of titanium.

United States Patent 1191 I I I 1111 3,920,745 I Floriani et al. Nov.18, 1975 1 PROCESS FOR THE CATALYTIC I FORE! N PATENTS OR APPLICATIONSHYDROGENATION 0F UNSATURATED 13 85] 3/ p 760/683 9 COMPOUNDS ANDCATALYST 690:582 10/1960 Canada 260/666 P EMPLOYABLE IN SUCH A PROCESS[75] Inventors: Carlo Floriani, Pisa; Giuseppe OTHER PUBLICATIONSFachinetti, Fauglia, both of Italy Bulletin of The Chemical Soc1ety ofJapan Vol. 39,

[73] Assign: San'Donato pp. 1l78ll82 (1966) The Homogeneous Hydrogena-Milanese Italy tion of Acetylenes by Dicyclopentadienyl titanium [22]Filed; O t, 16, 1974 dicarbonyl, Sonogoshira et al.

[21] App]. No.: 515,227

Primary Exarr'zinerDelbert E. Gantz Assistant Examiner-Juanita M. Nelson[30] Foreign Apphcamm Pnonty Data Attorney, Agent, or Firm-Ralph M.Watson, Esq.

Oct. 16, l973 Italy 30154/73 52 vs. C]. 260/683.9; 260/676 R; 260/666 Pa 51 Int. Cl. C07C 9/00; CO7C 5/02 [57] ABSTRACT [58] Field ofSearch..,.. 260/676, 683.9, 667, 666 P;

208/143 The present invention refers to a process for the catalytichydrogenation of unsaturated compounds using [56] References cited ascatalyst an acetylenic complex of titanium.

UNITED STATES PATENTS 3 Claims, N0 Drawings 3,663,635 5/1972 Lassall etal. 260/683.9 Y

1 PROCESS FOR THE CATALYTIC HYDROGENATION OF UNSATURATED COMPOUNDS ANDCATALYST EMPLOYABLE IN SUCH A PROCESS constituted by the reactionproduct thereof with an acetylenic compound, the obtained product has avery higher catalytic activity.

Therefore a first object of the present invention consists of ahydrogenation process of olefinic or acetylenic compounds carried out atroom temperature and at light hydrogen pressures in presence of acatalyst constituted by a complex of titanium with an acetylenicderivative and carbon monoxide.

A second object of the present invention is constituted by ahydrogenation catalyst having the formula CO R,

wherein R, and R may be hydrogen, alkyl, aryl or cycloalkyl radicalshaving up to 10 carbon atoms.

A third object of the present invention is constituted by the processfor the preparation of the abovesaid catalyst.

The hydrogenation process of unsaturated compounds according to thepresent invention involves the employment of a hydrogenation catalyst asabovesaid and is preferably carried out in solution of a solvent inertwith respect to the reagents and the reaction products.

Preferably it is carried out in presence of aliphatic, cycloalophatic oraromatic hydrocarbons provided that they are liquid at the reactiontemperature.

The reaction temperature may range from to 50C, preferably theoperations are performed at room temperature.

The hydrogen pressure is not a critical factor as to the hydrogenationreaction; however, for the procedure convenience, the process is carriedout at a pressure ranging from 1 to absolute atmospheres, preferably atthe atmospheric pressure.

The inventive hydrogenation reaction may be carried out starting fromany organic compound which have at least one ethylenic or acetylenicunsaturation and do not react with the catalyst.

According to what aforesaid the hydrogenation can be performed onolefines such as ethylene, propylene, butenes, pentenes, hexenes,cyclohexenes, heptenes I and the like, diolefins such asbutadiene,isoprene, phenylbutadiene, diphenylbutadiene, pentadienes,cyclooctadienes, acetylenic compounds such as methylacetylene,phenyl-acetylene, diphenyl-acetylene.

ln its turn, the catalyst employed in the inventive hydrogenationprocess, is obtained by simply reacting dicarbonyl dicyclopentadienyltitanium complex'with a ,compound having the formula R -C Ii C-R inwhich R and R have the abovesaid meanings.

The reaction is carried out in an inert solvent at temperature rangingfrom 0t'o 50C. The product, in such a way obtained, is fastly removedfrom the solvent.

However the invention willbe more understable examining the followingexamples,.which detail all opv erative formalities.

EXAMPLE 1 Preparation of Ph C (CO)Ticp 400 cc of heptane were added to amixture of Ticp (CO) (4.2 g) and Ph C (6.7 g) in the solid state. Thesolution, clear and stirred (25C by a thermostat), was continuosly Keptunder vacuum (lightly open water pump); a microcrystalline gold-yellowsolid began separating after four hours. After 24 hours the reaction wasstopped (final volume 500 cc). The solid was filtered and washed byheptane. Yield was 3.5 g.

Analysis: theoretical C 78.2 H 5.22 found C 78.20 H 5.25

v CO 2000 cm n.m.r. (C DQ multiplet singolet v C=C 1780 cm (Nujol) at2.9 1 (l0 H, Ph) at 5.0 -r (10 H. cp)

EXAMPLE 2 passing into the solution.

It was subjected to air in order to oxidize the catalyst which gave riseto substances insoluble in heptane. Through thin layer cromatography amain product was identified together with traces of dibenzyl arosen fromthe catalyst.

The raw product, after the evaporation of heptane, was againcrystallized from heptane and gave 1.2 g of product having a meltingpoint of 53 54C (scientific papers: 52 53C) which was also identifiedthrough N.M.R. way.

EXAMPLES 3 7 t The following examples refer to the hydrogenation ofvarious organic substrates at room temperature and pressure, carried outaccording to the formalities of the preceding example.

In the table we reported, for the sake of comparison, hydrogenationtests of the same organic substrated by using, as catalyst, theinventive compound and titanium diciclopentadienyl dicarbonyl.

The data clearly show our compound is a catalyst much more active thanthe known compound.

TABLE Catalyst hydrogenation in presence of Ti(C H (CO) or of Ti(C H)PhC PhXCO) Conditions: I atm. H Room temperature. heptane as solvent(50 cc) Olefin or mmoles TiCp (CO) TiCp (PhC- Ph)(CO) Sub/cat Reactionhydrogenated acetilenic commmoles mmoles ratio Time pound PhC I CPh 2.,80.77 3.6 3 hr 30 7: PhCH CH Ph 5.5 0.39 14.5 1-3 min 100% PhCH CH Phtrans-stylbenc 5.55 0.64 8.7 5 hr no reaction 5.55 0.34 16.3 min 100%PhCH CH Ph PhCH=CH-CH=CH- 6.95 0.77 9.0 3 hr no reaction 6.95 0.49 18.015 min 100% Ph(CH ),Ph cyclohexene 18.3 0.60 32.0 24 hr no reaction 18.30.39 47.0 14 hr 90 7t cyclohexene not tested n.d. l octene l octene 5005 min 100% octane What we claim 1. Process for the hydrogenation ofethylenically or acetylenically unsaturated hydrocarbons characterizedin that the reaction is carried out in the presence of a catalyst,having the formula kyl radicals having up to 10 carbon atoms.

0 to 50C.

3. Process according to claim 1 characterized in that C,H, T fi 25 thereaction is carried out in the presence of a solvent CSHS/ I inertthereto, generally selected from the saturated hydrocarbons.

in which R and R are hydrogen, alkyl, aryl or cycloal- 2. Processaccording to claim 1 characterized in that the reaction is carried outat temperatures ranging from

1. PROCESS FOR THE HYDRATION OF ETHYLENICALLY OR ACETYLENICALLYUNSATURATED HYDROCARBONS CHARACTERIZED IN THAT THE REACTION IS CARRIEDOUT IN THE PRESENCE OF A CATALYST, HAVING THE FORMULA
 2. Processaccording to claim 1 characterized in that the reaction is carried outat temperatures ranging from 0* to 50*C.
 3. Process according to claim 1characterized in that the reaction is carried out in the presence of asolvent inert thereto, generally selected from the saturatedhydrocarbons.